Oil-in-alcohol emulsified composition

ABSTRACT

The purpose of the present invention is to provide an oil-in-alcohol emulsified composition that the oil phase is uniformly and stably dispersed into an outer phase which is mainly comprised of a lower alcohol. 
     Accordingly, the oil-in-alcohol emulsified composition of the present invention comprising: (a) an oily component, (b) a lower alcohol, (c) water, and (d) an emulsifier which comprising one or more of polyether-modified silicones represented by the following general formula (1), ##STR1##  In the formula: A is a polyalkylene group shown as the general formula: --C 3  H 6  O(C 2  H 4  O) a  (C 3  H 6  O) b  R&#39; (where R&#39; is a group selected from the group of a hydrogen atom, an acyl group, and alkyl groups having a carbon number of 1 to 4, where a is an integer of 5 to 50, and where b is an integer of 5 to 50.); R is a methyl group or a phenyl group; m is an integer of 50 to 1,000; and n is an integer of 1 to 40.!.

This application is a 371 of PCT/JP96/01939 filed on Jul. 12, 1996.

TECHNICAL FIELD!

The present invention relates to an oil-in-alcohol emulsifiedcomposition and in particular, relates to the improvement of itssurfactant.

BACKGROUND ART!

In general, a hair cosmetic preparation is compounded with a largeamount of alcohol, in particular ethyl alcohol, as compared with acosmetic preparation which is applied in other regions. These loweralcohols are worked as a solvent of various ingredients and provide arefresh feeling and disinfectant property in the case where they areapplied on hair.

The term hair cosmetic preparation has a significant meaning as a hairdressing function, and polyalkylene glycol which has high alcoholsolubility is normally used for giving this hair dressing function.

On the other hand, emulsion type hair cosmetic preparations such as haircream, have attracted attention from because of the requirements forgiving hair gloss, softness, and moisture, and making it easier to comb.Emulsion type hair cosmetic preparations are compounded with an oilycomponent such as silicone oil, liquid paraffin, petrolatum, and thelike.

However, it is considerably difficult to make the various oilycomponents disperse and compound uniformly into lower alcohol basedcompositions.

Namely, the compositions referred to as an emulsified compositions ingeneral, mean the dispersion system of water and oil. For example, inthe case of preparing an oil-in-water emulsion, the composition and theamount of the oil phase are determined in first, and then, the type andthe amount of the emulsifier which is suitable, and the properemulsifying process are selected.

In the selection of this emulsifier, the concept of HLB which isexperimentally established by Griffin et al. However, this concept ofHLB is only related to the solubility of the surfactant in an oil-watersystem.

And, in general, the HLB of surfactant is prepared in the range of 7 to18 in an oil-in-water emulsion and 3 to 7 in a water-in-oil emulsionrespectively, and emulsification is performed by solubilizing thesurfactants into the oil phase or the water phase.

In order to obtain a stable emulsion with a nonionic surfactant whichchemically stable and which has a small possibility to degenerate otheringredients, it is necessary to combine a hydrophilic nonionicsurfactant and a lipophilic nonionic surfactant. And further, it isnecessary to arrange said surfactant to a boundary by enlarging theboundary area between the oil phase and the water phase by the usingstrong stirring power of a homogenizer and the like. In case of using aspecific type of surfactant and further compounding the surfactant in alarge amount, the stable emulsion can be obtained without using theabove-mentioned process. However, in rare occasions, an allergicreaction is observed in some people. So, in the case where thesurfactant is used in the above-mentioned cosmetic preparations, it isnecessary to select carefully the type and the amount of the surfactantadded.

And, in the case where the hydrophilic property of the hydrophilicnonionic surfactant is in extremely high (HLB is more than about 20),the ability of surface activity is decreased. So, even in the case wherea hydrophilic nonionic surfactant is compounded with a lipophilicnonionic surfactant, it is difficult to obtain a stable emulsion.

And further, in reference to the stability of the emulsion, the emulsionwhich is prepared by the conventional emulsifying process, is not somuch favorable in the stability at a high temperatures in general, sincethe cloudy point of the nonionic surfactant used is relative low.

And, in an oil-in-alcohol emulsified composition which comprises anexcessively large amount of alcohol with respect to an amount of waterin an outer phase, the evaluation of the surfactant by means of HLBmentioned above is difficult, and the stable emulsion system has notbeen obtained so far.

For example, Japanese Unexamined Patent Publication No. Sho 60-197610and Japanese Unexamined Patent Publication No. Sho 63-250311 disclosesexamples which are compounded silicone oil into a water phase whichcomprises 50% by weight or more of ethyl alcohol concentration. However,even in these compositions of prior art, it is necessary to add varioushumectants, and the ethyl alcohol concentration is limited to 50% byweight or less with respect to the water phase. So, the composition isfar from regarding as what is called an alcohol based composition.

DISCLOSURE OF INVENTION!

In view of the above-mentioned problems of the prior art, an object ofthe present invention is to provide an oil-in-alcohol emulsifiedcomposition where the oil phase is dispersed uniformly and stably intoan outer phase which is essentially comprised of a lower alcohol.

As a result of diligent studies of the inventors for attaining theabove-mentioned objects, it has been found that an oil-in-alcoholemulsified composition which is excellent in stability can be obtainedby using a specific polyether-modified silicone. Accordingly, thepresent invention has been accomplished.

Namely, an oil-in-alcohol emulsified composition in accordance with thepresent invention comprising: (a) an oily component; (b) a loweralcohol; (c) water; and (d) an emulsifier which comprising one or moreof polyether-modified silicones represented by the following generalformula (1), ##STR2## wherein: A is a polyalkylene group shown as thegeneral formula: --C₃ H₆ O(C₂ H₄ O)_(a) (C₃ H₆ O)_(b) R' (where R' is agroup selected from the group of a hydrogen atom, an acyl group, andalkyl groups having a carbon number of 1 to 4, where a is an integer of5 to 50, and where b is an integer of 5 to 50.); R is a methyl group ora phenyl group; m is an integer of 50 to 1,000; and n is an integer of 1to 40.!.

In said general formula, preferably, R is a methyl group.

In the composition of the present invention, preferably, m is 150 to1,000.

Also, in the composition of the present invention, preferably, the loweralcohol is comprised three times the amount or more of water.

Preferably, the lower alcohol is comprised 50% by weight or more.

Also, in the present invention, preferably, the compounding ratio of thepolyether-modified silicone to the lower alcohol is 1:9 to 5:5 in weightratio.

Also, preferably, the compositions of the present invention are haircosmetic preparation.

An oil-in-alcohol emulsified composition in accordance with the presentinvention is characterized in that the lower alcohol is comprised in anexcessive amount with respect to water, in particular, the oilcomposition is an oil-lower alcohol-water system that the lower alcoholis three times the amount or more of water, and it is characterized inthat one or more of polyether-modified silicones shown in the generalformula (1) is/are used.

Namely, an emulsified composition of the present invention is entirelydifferent from the conventional emulsification, it is an entirely newoil-in-alcohol emulsified composition which does not use hydrophilicnonionic surfactants, which rather uses the polyether-modified siliconewhich is gelated by contacting with water as only one emulsifier, andwhich is emulsified in an oily component at high alcohol concentrations.

In said general formula (1), as for an acyl groups of R', a formylgroup, an acetyl group, a propionyl group, a butyryl group, an acryroylgroup, a benzoyl group, a toluoyl group, and the like are exemplified.And, as for alkyl groups having a carbon number of 1 to 4, a methylgroup, an ethyl group, an i-propyl group, a n-propyl group, a t-butylgroup, a n-butyl group, and the like are exemplified.

In the case where a or b is less than 5 in a polyoxyalkylene group,polyether-modified silicone does not show sufficient surface activeeffect, and in the case where a or b is more than 50, the obtainedcomposition possess a sticky feeling.

The compounding amount of the polyoxyalkylene group in the molecule isnot particular limited. It is desirable to compound the polyoxyalkylenegroup more than 20% by weight with respect to whole amount of themolecule. This is because the thickening effect of thepolyether-modified silicone is remarkably decreased, in the case wherethe compounding amount of a polyoxyalkylene group is 20% by weight orless with respect to the whole amount of the molecule.

Also, m is an integer of 50 to 1,000, and n is an integer of 1 to 40.This is because that the emulsion stability is poor in the case where mis less than 50 and n is less than 1, And this is because the obtainedcomposition has a sticky feeling where m is more than 1,000 and n ismore than 40. Preferably, m:n is 200:1 to 5:1, and more preferably 60:1to 15:1.

The molecular weight of the polyether-modified silicone used in thepresent invention and its viscosity at 25° C. are not limited inparticular. The viscosity in the case of the polyether-modified siliconemade with 50% by weight aqueous solution of octamethyl tetrasiloxane orisoparaffin, is desirable to be within the range of 1,000 to 100,000cps, since the combination forms a particularly stable emulsion andpossess a dry feeling.

The compounding amount of the polyether-modified silicone used in thepresent invention is not limited in particular. Preferably, it is 1% byweight or more, and more preferably, 3% by weight or more. Alsopreferably, the compounding amount of the polyether-modified silicone is30% by weight or less, and more preferably, 20% by weight or less. Thisis because in the case where the compounding amount of thepolyether-modified silicone is less than 1% by weight, it is difficultto stably emulsify the composition, and in the case where thecompounding amount is more than 30% by weight, the obtained compositionpossesses a sticky feeling.

The type of the lower alcohol used in the present invention is notlimited in particular, and methanol or ethanol is preferable. And inconsidering the aspects of stability, ethanol is preferable.

Further, i-propanol, n-propanol, t-butanol, s-butanol, and the like aredifficult to emulsify, since these ingredients have a strong hydrophobicproperty. So, these ingredients are desirable to be used together withethanol.

Preferably, the compounding amount of the lower alcohol is three timesthe amount or more (weight ratio) with respect to the amount of water inthe composition. In the case where the amount of the lower alcohol isless than three times the amount, it is difficult to emulsify thesolution because the viscosity is increased since the whole system comesto gelation by the presence of the polyether-modified silicone.

Further, in view of the prior art teaching that is difficult to emulsifyoil-in-alcohol systems at high alcohol concentrations, it will beunderstood the significance of the present invention is where thecompounding amount of the lower alcohol is 50% by weight or more withrespect to the composition.

The oily components used in the present invention are not limited inparticular. The oily components such as liquid paraffin, squalane,lanolin derivatives, higher alcohol, various ester oils, avocado oil,palm oil, beef tallow, jojoba oil, silicone oil, polyalkylene glycolpolyether and oligo carboxylate compound, terpene type hydrocarbon oils,and the like are exemplified.

In the oil-in-alcohol emulsified composition of the present invention,in addition to the above-mentioned essential constituents, according toits object, various ingredients may be compounded within the quantityand the quality range as long as the effects of the present inventionare not spoiled. Examples of such ingredients include water solublepolyvalent alcohols such as ethylene glycol, propylene glycol,1,3-butylene glycol, glycerin, sorbitol, polyethylene glycol, and thelike; humectants such as hyaluronic acid, chondroitin sulfate,pyrrolidone carboxylate, and the like; UV-absorbent; UV-scatteringagent; resins such as acrylic resin, silicone resin,polyvinylpyrrolidone, and the like; proteins or protein decompositionproducts such as soybean protein, gelatin, collagen, silk fibroin,elastin, and the like, antiseptic agents such as ethyl paraben, butylparaben and the like, activating agents such as various amino acid,biotin, pantothenic acid derivatives, and the like; blood flowstimulants such as γ-oryzanol, sodium dextran sulfate, vitamin Ederivatives, nicotine derivatives and the like; antiseborrheic agentssuch as sulfur, thiantol, and the like; diluents such as ethanol,isopropanol, tetrachlorodifluoroethane, and the like; thickening agentssuch as carboxyvinyl polymer; drug; perfume; coloring agent, and thelike.

The oil-in-alcohol emulsified composition is used as various haircosmetic preparations such as general hair dressing preparations,shampoo agents, rinse agents, treatment agents, set agents, permanentwaving lotions, mascara, and the like.

And the composition also can be used for alcohol-based externalpreparations for skin which have a high alcohol concentration, e.g.,skin lotion, and the like.

BEST MODE FOR CARRYING OUT THE INVENTION!

In the following, the preferable embodiments of the present inventionare explained.

In the first place, the inventors studied about the emulsion stabilityin alcohol-based as compared with the following representiveoil-in-water type emulsifying process.

Conventional process 1

(1)Propylene glycol: 2.5

(2)Polyoxyethylene hydrogenated castor oil (60E.0): 1.0

(3)Ion-exchanged water: 11.5

(4)Dimethylpolysiloxane (n=3,000): 15.0

(5)Ethanol: 70.0

Process

The ingredient (2) and a part of the ingredient (3) were mixed into theingredient (1), and emulsified by adding the ingredient (4). After this,the ingredient (5) was added.

Conventional process 2

(1)Ion-exchanged water: 9.6

(2)Dimethylpolysiloxane (n=3,000): 15.0

(3)Isostearic acid: 0.4

(Trade name: ISOSTEARIC ACID PK, produced by KOKYU ALCOHOL CO.,LTD.)

(4)Imidazolinium betaine amphoteric surfactant: 5.0

(Trade name:OVAZOLINE 662-N, produced by TOHO KAGAKU K.K.)

(5)Ethanol: 70.0

Process

Emulsified by adding the ingredients (1), (2), (3), and (4), and then,the ingredient (5) was added.

Conventional process 3

(1)Dimethylpolysiloxane(n=3,000): 15.0

(2)Alkyl denatured carboxyvinyl polymer: 0.2

(Trade name: PEMULEN TR-2, B. F. GOODRICH COMPANY)

(3)Ion-exchanged water: 14.2

(4)Potassium hydroxide (10% aqueous solution): 0.6

(5)Ethanol: 70.0

Process

A part of the ingredient (3) was added to the mixture of the ingredients(1) and (2), and then, emulsified by adding the ingredient (4). Afterthis, the rest of the ingredient (3) was added, and further theingredient (5) was added to this.

Conventional process 4 to 6

All amounts of ethanol of said conventional process 1 to 3 were replacedwith ion-exchanged water, and emulsifying operation was performed by thesame processes as above.

Present emulsifying process

(1)Dimethylpolysiloxane (n=3,000): 15.0

(2)Polyether-modified silicone (Note 1): 5.0

(3)Ion-exchanged water: 10.0

(4)Ethanol: 70.0

Process

Emulsifying the rest of the ingredient (4) under stirring with theingredients (1), (2), and a part of the ingredients (3) and (4), afterthen adding the rest of the ingredient (3). ##STR3##

                  TABLE 1                                                         ______________________________________                                        Emulsifying process                                                                            Stability                                                    ______________________________________                                        Conventional process 1                                                                         Δ (creaming in a moment,                                                 and then demulsified)                                       Conventional process 2                                                                         × (demulsified in a moment)                            Conventional process 3                                                                         □ (aggregated in a moment)                        Conventional process 4                                                                         ◯                                                Conventional process 5                                                                         ◯                                                Conventional process 6                                                                         ◯                                                Present emulsifying process                                                                    ◯ (stable (at 50° C., in 3                ______________________________________                                                         months))                                                 

In Table 1, conventional process 1 used propylene glycol which has highsolubility with respect to ethanol. However, polyoxyethylenehydrogenated castor oil (surfactant) did not show a preferable emulsionstate by the reason that dimethylpolysiloxane was compounded as an oilycomponent, was creaming in a moment, and then it demulsified.

On the other hand, even though conventional process 2 used imidazoliniumbetaine amphoteric surfactant as general surfactant, it did not obtainany emulsifying action.

Further, in conventional process 3, an attempt was made to prepare astable dispersion system by thickening the emulsified composition withno common emulsifier, other than alkyl denatured carboxyvinyl polymerand potassium hydroxide. However, the aggregation occurred in this case,and the proper emulsified composition was not obtained.

On the other hand, in the case where all amounts of ethanol werereplaced with ion-exchanged water (conventional process 4 to 6) incorrespondence with said conventional process 1 to 3, emulsion stabilityin some degree was obtained. As a result of this, it was found thatethanol gives an extremely bad influence on emulsion stability.

On the other hand, when the emulsifying process of the present inventionwas used the polyether-modified silicone as an emulsifier, even in thecase where a large amount (70% by weight) of ethanol was compounded, theextremely stable emulsifying state was obtained.

And, the inventors paid attention to the emulsion stability givingeffect of the polyether-modified silicone in an ethanol-based emulsifiedcomposition, and they further conducted the following tests.

Selection of Polyether-Modified Silicone

Namely, the comparison of the emulsifying ability of thepolyether-modified silicone of the present invention and otherpolyether-modified silicones in Tables 2 to 5 will be shown.

Process of Each Composition

Any of the ingredients (1), (2), and (3) were mixed. The ingredients (4)and (5) were further added to this and stirred, after then emulsified byadding the ingredient (6).

                  TABLE 2                                                         ______________________________________                                        Basic formulation                                                             ______________________________________                                        (1)Dimethylpolysiloxane 6CS                                                                           24                                                    (2)Dimethylpolysiloxane (n = 3,000)                                                                   24                                                    (3)Polyester-modified silicone (Note 2)                                                               10                                                    (4)Ion-exchanged water   1                                                    (5)Ethanol (95%)         1                                                    (6)Ethanol (95%)        40                                                    ______________________________________                                         Note 2                                                                        ##STR4##                                                                 

The following Table 3 shows the test results of emulsion stability andstickiness in the case where the value of m, n, and b were fixed at 400,10, and 24 respectively and the value of a was changed in the generalformula (2) of Table 2 above.

                  TABLE 3                                                         ______________________________________                                        Test example   1       2      3     4    5                                    ______________________________________                                        Polyether-modified silicone                                                   m              400     400    400   400  400                                  n              10      10     10    10   10                                   a               3       5     24    47   60                                   b              24      24     24    24   24                                   Emulsion stability                                                                           ×◯                                                                  ◯                                                                        ◯                                                                       ◯                             Stickiness     ◯                                                                         ◯                                                                        ◯                                                                       ◯                                                                      Δ                              ______________________________________                                    

As is clear from Table 3, that emulsion stability was unfavorable in thecase where the value of a was 3. However, in the case where the value ofa was 5 to about 50, it showed favorable results in emulsion stabilityand stickiness. And in the case where the value of a was 60, it had nobig effect in emulsion stability. However, the obtained emulsifiedcomposition was not preferable, because the emulsion caused stickiness.As a result of this, it is understood that the value of a is preferably5 to 50.

And, in the case where the value of b was changed instead of the valueof a in the above-described test, almost same results were shown.

The following Table 4 shows the test results of emulsion stability andstickiness in the case where the value of n, a, and b were fixed at 10,24, and 24 respectively and the value of m was changed in the generalformula (2) of Table 2 above.

                                      TABLE 4                                     __________________________________________________________________________                Test example                                                                  6    7  8  9  10 11 12 13 14                                      __________________________________________________________________________    Polyether-modified silicone                                                   m           about 30                                                                           50 120                                                                              150                                                                              220                                                                              400                                                                              800                                                                              1000                                                                             2000                                    n           10   10 10 10 10 10 10 10 10                                      a           24   24 24 24 24 24 24 24 24                                      b           24   24 24 24 24 24 24 24 24                                      Emulsion stability                                                                        x    Δ*.sup.1                                                                   Δ*.sup.1                                                                   0  0  0  0  0  Δ                                 Stickiness  ∘                                                                      ∘                                                                    ∘                                                                    ∘                                                                    ∘                                                                    ∘                                                                    ∘                                                                    ∘                                                                    Δ                                 __________________________________________________________________________

As is clear from Table 4, in the case where the value of m was 30, itremarkably lacked emulsion stability. And, in the case where the valueof m was 50, emulsion stability was slightly improved, but the shelfstability at high temperatures was still unfavorable.

On the other hand, in the case where the value of m was 200 or more, itis understood that the emulsion stability together with the shelfstability at high temperatures were largely improved.

Accordingly, it is understood that the value of m is preferably 50 to1,000 and more preferably 150 to 1,000.

The following Table 5 shows the test results in the case where the valueof n was changed in the general formula (2) of Table 2 above.

                  TABLE 5                                                         ______________________________________                                                  Test example                                                                  15   16     17     18   19   20   21                                ______________________________________                                        Polyether-modified                                                            silicone                                                                      m           400    400    400  400  400  400  400                             n           0      1      3    10   30   40   50                              a           24     24     24   24   24   24   24                              b           24     24     24   24   24   24   24                              Emulsion stability                                                                        x      Δ                                                                              ∘                                                                      ∘                                                                      ∘                                                                      ∘                                                                      ∘                   Stickiness  --     ∘                                                                        ∘                                                                      ∘                                                                      ∘                                                                      Δ                                                                            x                               ______________________________________                                    

In Table 5, in the case where the value of n was 0, emulsion stabilitywas hardly observed. However, in the case where the value of n was 1, aslight stabilizing effect was observed, and in the case where the valueof n was 3 or more, a more remarkable emulsion stability was obtained.

However, in the case where the value of n was more than 40, it had atendency to be sticky, and it is understood that the preferable range ofn was 1 to 40, and more preferably, 3 to 30.

The Ratio of the Compounding amount of the Lower Alcohol and Water

Next, the test as shown in Table 6 was performed. And, a study about theratio of the compounding amount of the lower alcohol and water which waspreferable in the present invention was performed.

                  TABLE 6                                                         ______________________________________                                        Test example   22    23      24    25    26                                   ______________________________________                                        Dimethylpolysiloxane 6CS                                                                     24    24      24    24    24                                   Dimethylpolysiloxane                                                                         24    24      24    24    24                                   (n = 3,000)                                                                   Polyether silicone                                                                           10    10      10    10    10                                   (m:400, n:10, a:24, b:24)                                                     Ion-exchanged water                                                                           1     5      10    20    30                                   Ethanol         1     5      10    20    12                                   Ethanol        40    32      22     2    --                                   Ethanol/water  41      7.4     3.2   1.1   0.4                                Emulsion stability                                                                           ◯                                                                       ◯                                                                         ◯                                                                       Δ                                                                             Δ                              ______________________________________                                    

As is clear from Table 6, in the case where ethanol was compounded threetimes the amount or more (test examples, 22, 23 and 24) of ion-exchangedwater, the excellent emulsion stability was obtained. However, in thecase where ethanol was compounded within an amount which was equivalentto ion-exchanged water, it became difficult to emulsify since the wholeof system made a gelation and the viscosity was increased. Therefore, inthe present invention, the compounding amount of the lower alcohol ispreferably three times the amount or more of water in composition.

Next, the present invention will be clearly explained by listing theexamples and comparative examples. The present invention is not limitedto these. The compounding amount is % by weight.

EXAMPLE 1

Hair cream (treatment type)

(1)Dimethylpolysiloxane (n=3,000): 2.0

(2)Light liquid isoparaffin: 30.0

(3)Polyether-modified silicone (Note 3): 15.0

(4)Ethanol: 40.0

(5)Ion-exchanged water: 13.0

(6)Perfume: q.s.

(7)Paraben: q.s.

(8)Antioxidant: q.s.

Process

While stirring a mixture of the ingredients (1), (2), (3), and (5), anda part of the ingredient (4) by a homomixer at room temperature, amixture of the rest of the ingredient (4) and the ingredients (6), (7),and (8) was added. A hair cream was obtained. ##STR5##

EXAMPLE 2

Hair cream

(1)Amino-modified silicone: 1.0

(2)Dimethylpolysiloxane 6 cs: 3.0

(3)Polyether-modified silicone (Note 3): 10.0

(4)Ethanol: 76.0

(5)Ion-exchanged water: 5.0

(6)Perfume: q.s.

(7)Paraben: q.s.

(8)Antioxidant: q.s.

(9)Polyvinylpyrrolidone/polyvinyl acetate copolymer: 5.0

Process

While stirring a mixture of the ingredients (1), (2), (3), and (5), anda part of the ingredient (4) by a homomixer at room temperature, amixture of the rest of the ingredient (4) and the ingredients (6), (7),(8), and (9) was added. A hair cream was obtained.

EXAMPLE 3

Treatment mist

(1)Dimethylpolysiloxane 6 cs: 8.0

(2)Dimethylpolysiloxane (n=2,000): 8.0

(3)Ion-exchanged water: 3.0

(4)Ethanol: 75.9

(5)Perfume: q.s.

(6)Octyl methoxycinnamate: 0.1

(7)Polyether-modified silicone (Note 4): 5.0

Process

While stirring a mixture of the ingredients (1), (2), (3), and (7) and apart of the ingredient (4) by a homomixer at room temperature, a mixtureof the rest of the ingredient (4) and the ingredients (5) and (6) wasadded. A treatment mist was obtained. ##STR6##

EXAMPLE 4

Styling mist

(1)Dimethylpolysiloxane 6 cs: 4.0

(2)Dimethylpolysiloxane (n=1,000): 4.0

(3)Ion-exchanged water: 1.0

(4)Ethanol: 75.9

(5)Perfume: q.s.

(6)2-hydroxy-4-methoxybenzophenone: 0.1

(7)Polyether-modified silicone (Note 4): 5.0.

(8)Betain modified dialkylamino alkylacrylate copolymer: 10.0

(Trade name: YUKAFORMER AM75R205 S, produced by MITSUBISHI CHEMICALCORP.)

Process

While stirring a mixture of the ingredients (1), (2), (3), and (7) and apart of the ingredient (4) by a homomixer at room temperature, a mixtureof the rest of the ingredient (4) and the ingredients (5) and (6) wasadded. A styling mist was obtained.

EXAMPLE 5

Treatment lotion

(1)Dimethylpolysiloxane 20 cs: 15.0

(2)Dimethylpolysiloxane (n=5,000): 15.0

(3)Ion-exchanged water: 5.0

(4)Ethanol: 49.9

(5)Perfume: q.s.

(6)Octyl methoxycinnamate: 0.1

(7)Polyether-modified silicone (Note 2): 15.0

Process

While stirring a mixture of the ingredients (1), (2), (3), and (7) and apart of the ingredient (4) by a homomixer at room temperature, a mixtureof the rest of the ingredient (4) and the ingredients (5) and (6) wasadded. A treatment lotion was obtained.

EXAMPLE 6

Styling lotion

(1)Dimethylpolysiloxane 6 cs 3.0

(2)Dimethylpolysiloxane (n=1,000): 3.0

(3)Ion-exchanged water: 1.0

(4)Ethanol: 80.9

(5)Perfume: q.s.

(6)2-hydroxy-4-methoxybenzophenone: 0.1

(7)Polyether-modified silicone (Note 2): 3.0

(8)Polyvinylpyrrolidone/polyvinyl acetate copolymer: 7.0

(9)Polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer: 2.0

Process

While stirring a mixture of the ingredients (1), (2), (3), and (7) and apart of the ingredient (4) by a homomixer at room temperature, a mixtureof the rest of the ingredient (4) and the ingredients (5), (6), (8), and(9) was added. A styling lotion was obtained.

EXAMPLE 7

Treatment mist

(1)Dimethylpolysiloxane 6 cs: 10.0

(2)Dimethylpolysiloxane (n=2,000): 10.0

(3)Ion-exchanged water: 3.0

(4)Ethanol: 71.9

(5)Perfume: q.s.

(6)Octyl methoxycinnamate: 0.1

(7)Hydrolized woolkeratin (Average molecular weight 1000): 0.1

(8)Polyether-modified silicone (Note 3): 5.0

Process

While stirring a mixture of the ingredients (1), (2), (3), and (8) and apart of the ingredient (4) by a homomixer at room temperature, a mixtureof the rest of the ingredient (4) and the ingredients (5), (6), and (7)was added. A treatment mist was obtained.

COMPARATIVE EXAMPLE 1

Hair cream (treatment type)

(1)Carrageenan: 1.0

(2)Polyoxyethylene hydrogenated castor oil (60E.0): 1.0

(3)Carboxyvinyl polymer: 0.6

(Trade name: CARBOPOL 940, produced by B. F. GOODRICH COMPANY)

(4)Dimethylpolysiloxane (n=1,000): 5.0

(5)Triethanolamine: q.s. (pH7.5)

(6)Glycerin: 2.0

(7)Perfume: q.s.

(8)Octyl methoxycinnamate: 0.1

(9)Ethanol: 25.0

(10)Ion-exchanged water: 65.3

Process

The ingredients (2) and (4) were emulsified by adding the ingredient (6)(emulsion parts).

After dissolving uniformly by adding the ingredients (1) and (3) to theingredient (10), the emulsion parts were mixed into a mixture which wasobtained by adding the ingredients (5), (7)-(9). A hair cream treatmentwas obtained.

COMPARATIVE EXAMPLE 2

Hair cream (treatment type)

(1)Isoparaffin: 10.0

(2)Dimethylpolysiloxane: (n=3,000): 5.0

(3)Diglyceryl diisostearate: 20.0

(4)Dextrin fatty acid ester: 1.5

(5)Dimethyl distearyl ammonium hectorite: 1.5

(6)Ion-exchanged water: 56.4

(7)Glycerin: 4.0

(8)Polyethylene glycol 6000: 0.5

(9)Carboxyvinyl polymer: 0.5

(Trade name: CARBOPOL 940, produced by B. F. GOODRICH COMPANY)

(10)Carrageenan: 0.5

(11)Sodium hydroxide: 0.1

Process

The ingredients (1) to (8) were emulsified by mixing and stirring. Thenthe ingredients (9) to (11) were added, and a hair cream was obtained.

COMPARATIVE EXAMPLE 3

Treatment mist

(1)Decamethyl cyclopentasiloxane: 6.0

(2)Octamethyl cyclotetrasiloxane: 4.0

(3)Dimethylpolysiloxane (n=1,000): 3.0

(4)1,3-Butylene glycol: 3.0

(5)Polyoxyethylene hydrogenated castor oil (60E.0): 2.0

(6)Ethanol: 5.0

(7)Ion-exchanged water: 76.0

(8)Betain modified dialkylamino alkylacrylate copolymer: 1.0

(Trade name: YUKAFORMER AH75R205 S, produced by MITSUBISHI CHEMICALCORP.)

(9)Perfume: q.s.

Process

The ingredient (3) was dissolved into a mixture of ingredients (1) and(2). The mixture was emulsified by adding a mixture of the ingredients(4) and (5). And then, the ingredients (6), (7), (8), and (9) were mixedinto this.

COMPARATIVE EXAMPLE 4

Set lotion

(1)Polyvinylpyrrolidone/polyvinyl acetate copolymer: 5.0

(2)Cetyl-2-ethylhexanoate: 1.0

(3)Stearyl trimethyl ammonium chloride: 0.3

(4)Ethanol: 70.0

(5)Ion-exchanged water: 23.7

(6)Perfume: q.s.

Process

The ingredients (4) and (5) were stirred and dissolved. The ingredients(1) to (3), and (6) were further dissolved into this, and set lotion wasobtained.

<Evaluation results>

Evaluation of feeling/hair style

After wetting a strand of human hair by water which was uniformlyarranged the roots and the top of the hair, 2.0 g of hair set agentcomposition was applied to the strand and a hair style was finished by10 beauty experts. Then the organoleptic evaluation was done about (B)less stickiness after applied to drying, (C) smoothness in applying, and(D) smoothness after drying.

The evaluation has been done by finding the average point on the basisof following evaluation point. The test results are shown in Table 7 onthe basis of following evaluation results display.

1 Evaluation point

+3: Pretty good

+2: Good

+1: Slightly good

0:Normal

-1: Slightly bad

-2: Bad

-3: Extremely bad

2 Display of evaluation results

XX: Less than -2

X: -2 or more, less than -1

Δ: -1 or more, less than 0

□: 0 or more, less than +1

∘: +1 or more, less than +2

⊚: +2 or more

                  TABLE 7                                                         ______________________________________                                                                 Comparative                                                   Example         example                                                       1   2     3     4   5   6   7   1   2   3   4                        ______________________________________                                        Smallness of sticki-                                                                     ⊚                                                                    ⊚                                                                    ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  Δ                                                                           xx  Δ                                                                           x                      ness                                                                          Smoothness in                                                                            ⊚                                                                    ⊚                                                                    ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ∘                                                                     Δ                                                                           ∘                                                                     □           applying                                                                      Smoothness after                                                                         ⊚                                                                    ⊚                                                                    ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  ⊚                                                                  Δ                                                                           Δ                                                                           □                                                                      x                      drying                                                                        ______________________________________                                    

The oil-in-alcohol hair cosmetic preparation in accordance with thepresent invention is excellent in emulsion stability and is extremelyexcellent in feeling of use. It has less stickiness and it can besmoothly applied.

We claim:
 1. An oil-in-alcohol emulsified composition comprising:(a) anoily component, (b) a lower alcohol, (c) water, and (d) an emulsifierwhich comprising one or more of polyether-modified silicones representedby the following general formula (1): ##STR7## wherein A is apolyalkylene group shown as the general formula: --C₃ H₆ O(C₂ H₄ O)_(a)(C₃ H₆ O)_(b) R' (wherein R'is selected from the group consisting of ahydrogen atom, an acyl group, and an alkyl group having a carbon numberof 1 to 4, a is an integer of 5 to 50, and b is an integer of 5-50); Ris a methyl group or a phenyl group; m is an integer of 150 to 1,000;and n is an integer of 1 to
 40. 2. An oil-in-alcohol emulsifiedcomposition comprising:(a) an oily component, (b) a lower alcohol, (c)water, wherein the weight ratio of said lower alcohol to water is atleast 3:1, and (d) an emulsifier which comprising one or more ofpolyether-modified silicones represented by the following generalformula (1): ##STR8## wherein A is a polyalkylene group shown as thegeneral formula: --C₃ H₆ O(C₂ H₄ O)_(a) (C₃ H₆ O)_(b) R' (wherein R' isselected from the group consisting of a hydrogen atom, an acyl group,and an alkyl group having a carbon number of 1 to 4, a is an integer of5 to 50, and b is an integer of 5-50); R is a methyl group or a phenylgroup; m is an integer of 50 to 1,000; and n is an integer of 1 to 40.3. An oil-in-alcohol emulsified composition according to claim 2,wherein the lower alcohol is comprised 50% by weight or more.
 4. Anoil-in-alcohol emulsified composition comprising:(a) an oily component,(b) a lower alcohol, (c) water, and (d) an emulsifier which comprisingone or more of polyether-modified silicones represented by the followinggeneral formula (1): ##STR9## wherein A is a polyalkylene group shown asthe general formula: --C₃ H₆ O(C₂ H₄ O)_(a) (C₃ H₆ O)_(b) R' (wherein R'is selected from the group consisting of a hydrogen atom, an acyl group,and an alkyl group having a carbon number of 1 to 4, a is an integer of5 to 50, and b is an integer of 5-50); R is a methyl group or a phenylgroup; m is an integer of 50 to 1,000; and n is an integer of 1 to 40,wherein the weight ratio of said polyether-modified silicon to saidlower alcohol is 1:9 to 5:5.